CN106008776B - Ring-alkylated styrenes/isoolefin polymer preparation method - Google Patents
Ring-alkylated styrenes/isoolefin polymer preparation method Download PDFInfo
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- CN106008776B CN106008776B CN201610343716.0A CN201610343716A CN106008776B CN 106008776 B CN106008776 B CN 106008776B CN 201610343716 A CN201610343716 A CN 201610343716A CN 106008776 B CN106008776 B CN 106008776B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
Abstract
The present invention relates to ring-alkylated styrenes/isoolefin polymer preparation methods.The method includes providing the feed stream into reactor first.Various feed streams provide monomer, Polar diluents or the Polar diluents mixture and catalyst system for entering reactor.In the reactor, feed stream is in contact with each other so that monomer forms polymer in stable slurry, and wherein amount of the polymer in the slurry generates the slurry concentration for being greater than 22wt%.Molal quantity/mole initiator ratio of polymer is formed by the range of 0.25-4.0 moles of polymer/mole initiator.
Description
The application is application No. is 201180026851.8, and the applying date is on April 27th, 2011, entitled " alkyl
The divisional application of the application for a patent for invention of styrene/isoolefin polymer preparation method ".
Cross reference to related applications
This application claims the equity for the United States serial 12/791,520 that on June 1st, 2010 submits, the disclosures of the document
Content is fully introduced into herein incorporated by reference.
Technical field
The present invention relates to a kind of novel catalyst system, the caltalyst is tied up in method for continuous slurry polymerization in one kind
Or styrene/isoolefin copolymers reactor slurry is improved in the preparation of the random copolymer of a variety of isoolefin monomers and styrene
The heat-transfer capability of process system.
Background technique
Isobutylene-isoprene polymer is well-known since nineteen thirties.They are being stretched
Or there is good air impermeability and high-caliber resiliency when compression.These polymer are widely used in entire tire and medicine
In product industry.The copolymer passes through cationic slurry phase polymerisation process using the catalyst comprising lewis acid and initiator big
It is prepared at about -95 DEG C.Lewis acid, such as alkyl aluminum and aluminium chloride, are widely used in laboratory test and commercial size is raw
In production.Initiator, such as water and anhydrous HCl, are widely used.
Industry generally received the extensive use of slurry phase polymerisation process with prepared in diluent butyl rubber, gather it is different
Butylene and other similar polymer, the diluent dissolution monomer and catalyst but not dissolution polymer product.For manufacture
Traditional butyl rubber, i.e. isobutylene-isoprene copolymer, the slurry phase polymerisation process provide many other advantages, such as
With in polymerisation in solution only compared with the concentration of about 8%-12%, about 26%-37% is obtained by volume in reaction mixture
The polymer concentration obtained.The acceptable compared with low viscosity of polymer material is obtained, allows heat of polymerization more effectively by surface
Heat exchange removes.Potential challenge related with slurry polymerization is discussed in U.S. Patent number 6,939,933.
Isobutene-p-methylstyrene (IPMS) polymer is also known.They by with isobutylene-isoprene
The similar method of polymer is manufactured using similar initiation system, and is also used for tire and medicine trade.However, and isobutyl
Alkene-isoprene copolymer is compared, IPMS polymerization there are many difficult, and these it is difficult using higher level to methylbenzene second
Become to aggravate when alkene (PMS) comonomer.These difficulties include: reaction temperature and flash gas (liquid reactor composition)
Unstability；The unstability of Mooney viscosity control；Lower than desirable monomer-product yield；(especially by rubber fouling
It is around reactor cycles pump) it is caused higher than desirable heating rate (warm-up rate)；Lower than desirable
Operability limitation to slurry concentration；The shorter reactor operation period under comparable conditions；It is higher under comparable conditions
Slurry Viscosity；Poor and more unstable response with reactor to control parameter.Due to these difficulties, IPMS is prepared in history
Copolymer is more much more difficult and more expensive than conventional isobutylene-isoprene copolymer.Currently, these undesirable techniques
Characteristic is handled by limited throughput, PMS content or both combination.
Commercially, the preparation of IPMS copolymer is limited to the slurry concentration of about 20wt% polymer.Described value is significantly low
The value observed by for traditional isobutylene-isoprene copolymer, traditional isobutylene-isoprene copolymer can be with
It is operated at the 26-37wt% recorded above.The operation limitation of IPMS polymerization seems to be attributed to high Slurry Viscosity and be led
The heat transfer of the difference of cause.In addition, being usually subjected to substance fouling during initial polymerization.Improve the concentration and stability of IPMS slurry
Method can be improved reactor productivity and reduce the cost for preparing these polymer.
Summary of the invention
Summary of the invention
The method of polymer the present invention relates to preparation derived from least one isoalkene and alkyl-styrene, wherein institute
The slurry polymerization for stating polymer occurs under the following conditions: the condition makes the slurry generated in the reactor be stable
Slurry so that slurry concentration can be improved and obtain the production of resulting polymers and the improvement of output.
Therefore, disclosed herein is be used to prepare derived from C4-C7The polymerization of isoolefin monomer and alkyl-styrene monomer
The polymerization of object.The method includes first providing feed stream in reactor.Various feed streams are by monomer, polarity
Diluent or Polar diluents mixture and catalyst system are provided into the reactor.In the reactor, the original
Material stream is in contact with each other so that the monomer forms polymer in slurry, wherein volume production of the polymer in the slurry
The raw slurry concentration for being greater than 22wt%.The slurry is preferably stable slurry, and " stable slurry " is defined as following slurry: its
It is capable of stirring, runny fluid, it is opposite with high viscosity and the fluid for being difficult to stir.
In the one aspect of the invention disclosed, the catalyst system for supplying the reactor includes lewis acid and draws
Send out agent.Lewis acid can be for general formula RnMX3-nThe 13rd race's lewis acid, wherein M is the 13rd race's metal, and R is selected from C1-
C12Alkyl, aryl, aralkyl, alkaryl and naphthenic base monovalent hydrocarbon；N is the integer from 0 to 3；X be independently selected from fluorine,
The halogen of chlorine, bromine and iodine.Alternatively, the lewis acid can be selected from ethylaluminum sesquichloride (ethyl aluminum
Sesquichloride), aluminium bromide, boron chloride, diethylaluminum chloride, chlorodimethylalumiu and di-isobutyl aluminum chloride and it
Mixture.
In another aspect of the invention, it can also be fed by oxygenatedchemicals (oxygenate) or containing ionic species
The reactor.The oxygenatedchemicals can provide in catalyst feed stream, raw material monomer stream, or individually inject
In reactor.In an aspect, the oxygenatedchemicals is alcohol or ester.
Disclosed in of the invention one in aspect, the isoolefin monomer to be polymerized is isobutene, isobutene, 2- first
Base-l- butylene, 3-methyl-1-butene, 2- methyl-2-butene, 1- butylene, 2- butylene, methyl vinyl ether, indenes, vinyl three
Methyl-monosilane, hexene or 4-methyl-1-pentene.In another aspect, the alkyl-styrene is derived from C1-C7Alkyl.?
Another aspect, additional monomer, such as C4-C14Polyene is also added in reactor to form terpolymer.
There is disclosed herein be used to prepare derived from C4-C7The polymer of isoolefin monomer and alkyl-styrene monomer gathers
Conjunction method, wherein being formed by the ratio between mole of polymer and initiator in 0.25-3.0 moles of polymer/mole initiator
In range.The method includes first providing feed stream in reactor.Various feed streams are by monomer, Polar diluents
Or Polar diluents mixture and the catalyst system comprising lewis acid and initiator are supplied to the reactor.Described anti-
It answers in device, the feed stream is in contact with each other so that the monomer forms polymer in slurry.
There is disclosed herein the isoolefin-alkylstyrene polymer manufactured by any method discussed above.It is described
Polymer can also include C4-C14Unit derived from polyene.The polymer can be further by halogenation, or additionally, quilt
Functionalization.The polymer or its functional derivative can be blended to generate elastic composition or heat with various components
Thermoplastic elastic composition.The annexing ingredient includes, but are not limited to: a) at least one to be selected from calcium carbonate, clay, mica, two
Silica, silicate, talcum, titanium dioxide, starch, wood powder, carbon black or their mixture filler；B) at least one inorganic
Nanoclay or nanoclay；C) at least one processing oil；D) at least one to be selected from plastic body, polybutene, poly alpha olefin
The processing aid of oil or their mixture；E) at least one curing agent；F) auxiliary elastomer；G) thermoplastic resin；Or h) a-g
Any combination.
The disclosed polymer can be used for any composition, then the composition is directly used as tire flap, wheel
Tire capsule (a tire bladder), curing bag (a curing bladder), hose, conveyer belt or drug plug or as it
In component.
Detailed description of the invention
Method the present invention relates to catalyst system and preparation comprising the polymer to monomer derived from ring-alkylated styrenes.?
It is found that a kind of improved catalyst system and method, are as general as isoolefin-alkylstyrene copolymer, especially isoolefine
The commercial slurry polymerization of the p- ring-alkylated styrenes of hydrocarbon-(IPAS) copolymer provides many unexpected advantages.This new catalytic
Agent system includes lewis acid as described in more detail below.
Each specific embodiment, modification and embodiment of the invention will now be described, including in order to understand the present invention
Embodiment used by preferred embodiment and definition.In order to determine abuse, the range of this " invention " refers to appended reality
Apply any one or more of scheme, including they equivalent and element or with those of the listed limit being equal
System.
Definition
It is defined as follows suitable for presently described invention described.
Term as used herein " catalyst system " refers to and including for being catalyzed olefinic type monomers polymerization of the invention
Any lewis acid or other metal complexes and initiator as described below and other minor catalyst components.
" slurry " refers to comprising monomer, lewis acid, initiator and from certain body of the polymer of diluent precipitating
Long-pending diluent." slurry concentration " is that the weight percent-reaction monomers of these reaction monomers account for slurry, dilute
Release agent, unreacted monomer and catalyst system total weight weight percent.
" polymer " can be used to refer to homopolymer, copolymer, interpretation, terpolymer etc..Similarly, copolymer can refer to
Including at least two monomers, optionally there is the polymer of other monomers.
When claiming polymer to include monomer, the monomer is present in the derivative form of the polymerized form of monomer or monomer
In polymer.However, phrase " including described (corresponding) monomer " is waited to be used as and be write a Chinese character in simplified form for ease of reference,.Similarly, work as catalyst
When component is described as the neutral stable form comprising component, it will be understood by those skilled in the art that the ionic species of component is and monomer
Reaction is in the form of generating polymer.
" elastomer based on isobutene " or polymer refer to comprising repetitive unit of at least 70mol% from isobutene
Elastomer or polymer.
" hydrocarbon " refers to the segment of the main molecule comprising hydrogen and carbon atom or molecule.In some embodiments, hydrocarbon also wraps
Include the halogenation pattern of hydrocarbon and comprising heteroatomic pattern.
" alkyl " refer to one or more hydrogen are seized from the structural formula of alkane and derived from the alkane alkane group,
For example, methyl (CH3) or ethyl (CH3CH2) etc..
" rubber " refers to the composition for meeting any polymer or polymer that following A STM D1566 is defined: " can be from
Big deformation restores, and can with or it is modified to it in boiling solvent essentially insoluble (but can be swollen) shape
Material ... the " of state." elastomer " is the term that can be used interchangeably with term " rubber ".Elastic composition refers to comprising extremely
A kind of any composition of few elastomer as defined above.
Monomer
According to the present invention, applicant have discovered that it is a kind of for polymerizeing isoalkene containing 4-7 carbon atom and to alkylbenzene
The improved polymerization system of vinyl monomer.A preferred embodiment according to the present invention, the method are generated comprising about
The copolymer of the ring-alkylated styrenes of the isoalkene of 80-99.5wt% and about 0.5-20wt%.Glass is also prepared according to another
The embodiment of shape or plastic material, the copolymer include the isoalkene and about 0.5-90wt% of about 10-99.5wt%
Ring-alkylated styrenes.
The isoalkene is C4-C7Compound, their non-limiting example are compound such as isobutenes
(isobutylene), isobutene (isobutene), 2-methyl-1-butene alkene, 3-methyl-1-butene, 2- methyl-2-butene, 1-
Butylene, 2- butylene, methyl vinyl ether, indenes, vinyl trimethylsilane, hexene and 4-methyl-1-pentene.In some embodiment party
In case, may exist auxiliary alkene, such as C4-C14Polyene.The example of applicable polyene is isoprene, butadiene, 2,3-
Dimethyl -1,3- butadiene, laurene, 6,6- dimethyl-fulvene, hexadiene, cyclopentadiene and pentadiene.
The ring-alkylated styrenes is the styrene replaced, wherein being substituted by C1-C7Alkyl.In another embodiment, benzene
Alkyl on ethylene, which replaces, to be occurred in o-, m- or contraposition.In one embodiment, the ring-alkylated styrenes is methylbenzene second
Alkene.In another embodiment, the ring-alkylated styrenes is p-methylstyrene.
Catalyst system
As has been noted, limit of the polymerization of isoalkene and ring-alkylated styrenes by slurry concentration too low in reactor
System.It has been unexpectedly discovered that being pressed from both sides in the weight fraction and the reduction particle in sludge particles by improving polymer
Attached diluent generates less moles of polymer/mole initiator catalyst system and generates more less viscous slurry.Pass through
The amount that attached diluent is pressed from both sides in sludge particles is reduced, volume fraction of the particle in slurry reduces, to reduce identical in slurry
Slurry Viscosity under polymer weight fractin.It is thus possible to improve polymer weight fractin in reactor is with by Slurry Viscosity
The maximum restored into reactor can operate level.Whole result is the raising of reactor output and polymer production amount.
Mole/mole initiator of polymer produced in the present invention is no more than 4 moles of polymer/mole initiation
Agent.Alternatively, polymer/initiator ratio is in the range of 0.25-4.0 moles of polymer/mole initiator.In another reality
It applies in scheme, the system generates 0.25-3.0 moles of polymer/mole initiator.In another embodiment, the body
System generates 0.25-2.5 moles of polymer/mole initiator.In yet another embodiment, the system generates 0.5-2.5 and rubs
That polymer/mole initiator.
Generating less moles of polymer/mole initiator catalyst system includes the weaker road in conjunction with initiator
Lewis acid.When being added in polymerisation medium by oxygenatedchemicals or containing ionic species, also can be used in conjunction with initiator
Stronger lewis acid.While not wishing to be bound by theory, it is preferred that selection maximizes the ionic nature of slurry
Catalytic component.
Lewis acid
Desirable catalyst be the metal based on the periodic table of elements the 4th, 13 and 15 races, including boron, aluminium, gallium, indium,
Titanium, zirconium, tin, vanadium, arsenic, antimony and bismuth lewis acid.In one embodiment, the metal is aluminium, boron and titanium, and wherein aluminium is
Preferably.In the practice of the method for the present invention, cause less alkylation and branching and higher using weaker lewis acid
Monomer conversion rate.
13rd race's lewis acid has general formula RnMX3-n, wherein " M " is the 13rd race's metal, R is selected from C1-C12Alkyl, virtue
Base, aralkyl, alkaryl and naphthenic base monovalent hydrocarbon；N is the integer from 0 to 3；X is independently selected from fluorine, chlorine, bromine and iodine
Halogen, preferred chlorine.Term " aralkyl " refers to that " base " is located at alkyl containing the group of both aliphatic structure and aromatic structure
On position.Term " alkaryl " refers to that " base " is located on aryl position containing the group of both aliphatic structure and aromatic structure.
Weaker lewis acidic non-limiting example includes aluminium bromide, boron chloride, ethylaluminum sesquichloride (Et1.5AlCl1.5Or
EASC), diethylaluminum chloride, chlorodimethylalumiu and di-isobutyl aluminum chloride or their mixture.Stronger lewis acid
Non-limiting example include ethyl aluminum dichloride (EtAlCl2Or EADC) and diethylaluminum chloride or their mixture.
4th race's lewis acid has formula M X4, wherein M is group-4 metal, and X is ligand, preferably halogen.Non-limiting reality
Example includes titanium tetrachloride, zirconium chloride or tin tetrachloride.
15th race's lewis acid has formula M Xy, wherein M is the 15th race's metal, and X is ligand, preferably halogen, y be from 3 to
5 integer.Non-limiting example includes vanadium tetrachloride and antimony pentafluoride.
Initiator
An embodiment according to the present invention, lewis acid catalyst are used in combination with initiator.The initiator can
To be that those generate slow, gradually initiation and including several polarity in the equilibrium response of catalyst system such as water or HCl
The initiator of complex compound.Alternatively, the initiator is that those can be pre- with selected lewis acid in suitable diluent
It is first complexed with generation and carbonThe complex compound of ion pair balance, the carbonIon pair rapidly forms growth in the reactor
Polymer chain；This initiator generates quick, simple polymerization in the reactor to be caused." faster " initiator is
Greater than C4Tertiary halide, wherein the initiator have general formula (A):
Wherein X is halogen；R1Selected from C1-C8Alkyl and C2-C8Alkenyl；R3Selected from C1-C8Alkyl, C2-C8Alkenyl and octadecyloxy phenyl
Base；R2Selected from C4-C200Alkyl, C2-C8Alkenyl, phenyl, phenylalkyl, alkyl phenyl, C3-C10Naphthenic base and
Wherein X is halogen；R5Selected from C1-C8Alkyl and C2-C8Alkenyl；R6Selected from C1-C8Alkyl, C2-C8Alkenyl and octadecyloxy phenyl
Base；R4Selected from phenylene, xenyl, α, ω-diphenyl alkane and-(CH2)n, wherein n is the integer of 1-10；Wherein R1、R2
And R3Adamantyl or borneol ring system can also be formed, the X group is in tertiary carbon position.
The above general structure group (B) replaces the R in general formula (A)2It generates following general formula (C):
Wherein X, R1、R3、R4、R5And R6As defined above.The compound indicated by general structure (C), which includes two, to be solved
From halide and can consider be only those by general structure (A) indicate compound compound (multiple).
When it is desirable that generating branched copolymers, using multiple functionalized initiator, but mono- and difunctional's initiator is to basic
It is preferred for the preparation of upper linear straight copolymer.
In a desirable embodiment of structure (A), the initiator is the low of the isobutene such as structure (D)
Polymers:
Wherein X is halogen, and the value of m is from 1 to 60 and their mixture.In another embodiment, m
It is from 2 to 40.This structure is also described as the polyisobutene of tertiary alkyl chlorine sealing end, has in one embodiment up to
2500 Mn, in another embodiment up to 1200 Mn.
For example, representative initiator includes compound such as 2- acetyl group -2- phenyl-propane, i.e. acetic acid cumyl ester；2-
Methoxyl group -2- phenyl-propane, i.e. cumyl methyl-ether；Isosorbide-5-Nitrae-two (2- methoxyl group -2- propyl) benzene, that is, two (cumyl methyl ethers)；
The chloro- 2- phenyl-propane of cumyl halide, especially chloride, i.e. 2-, i.e. chlorination cumyl (the chloro- 1- Methylethyl of 1-) benzene；1,4-
Two (the chloro- 2- propyl of 2-) benzene, i.e., two (chlorination cumyls)；1,3,5- tri- (the chloro- 2- propyl of 2-) benzene, that is, three (chlorination cumyls)；Aliphatic series
Halide, especially chloride, i.e. 2- chloro- 2,4,4- trimethylpentanes (TMPCl), 2- bromo- 2,4,4- trimethylpentanes
(TMPBr), the chloro- 2,4,4,6- tetramethyl base heptane of 2,6- bis-；Cumyl and aliphatic hydroxide radical compound such as 1,4- bis- ((2- hydroxyl -2- third
Base)-benzene), 2,6- dihydroxy -2,4,4,6- tetramethyls-heptane, 1- chlorine adamantane and 1- bornyl chloride alkane (bornane), the tertiary fourth of 5-
(the chloro- 1- Methylethyl of the 1-) benzene of base -1,3- two and similar compound.Other non-limiting examples of suitable initiator are hydrocarbon
The cumyl ester and alkyl cumyl ether of acid.Other suitable initiator may refer to U.S. Patent number 4, and 946,899, it is special for the U.S.
Sharp practice purpose is incorporated herein by reference.These initiators are usually C5Or bigger uncle or allylic alkyl or benzyl class halogen
Compound and may include multiple functionalized initiator.The desirable example of these initiators includes: TMPCl, TMPBr, 2,6-
Two chloro- 2,4,4,6- tetramethyl base heptanes, chlorination cumyl and chlorination or bromination " two-" and " three-" cumyl.In another embodiment party
In case, initiator is the polyisobutene of the chlorination tertiary alkyl sealing end of the Mn (number-average molecular weight) with up to 2500.
In one embodiment, TMPCl is following obtained: isobutene dimer being dissolved in methyl chloride, then
Anhydrous HCl is added to form alkyl chloride.Then as obtained by nitrogen purges excessive HCl and use TMPCl is in methyl chloride
Solution is as the initiator stream in the continuous apparatus for preparing butyl polymer.In an embodiment of business type method,
TMPCl stream and cold methyl chloride (chloromethane) stream and alkyl aluminum stream are mixed to form catalyst system.Then will
Be used in continuous flowing stirred-tank reactor (" CFSTR ") of this stream injection condition more possible than before this it is more controllable and
Isobutene-ring-alkylated styrenes polymer is prepared under conditions of economy.
Molar ratio suitable for lewis acid and initiator at this to all embodiments disclosed by the invention is rubbed 1.5
In the range of your lewis acid/mole initiator to 30 moles of lewis acid/mole initiators.It can also for all embodiments
With the molar ratio of lewis acid and initiator is in the range of 1.5 to 20 or 2 to 20.
Oxygenatedchemicals/contain ionic species
If lewis acid is stronger acid, the Louis can be added to by oxygenatedchemicals and containing ionic species
In this acid/initiator mixture.These additives of catalyst system include pure and mild ether.When using oxygenatedchemicals, in addition to
Except catalyst stream, they can also be added in polymerisation medium by any stream, including the straight of oxygenatedchemicals itself
Connect injection.The concentration range of oxygenatedchemicals is 15-0.5wt ppm or lower or 8-1ppm, is based on reactor content.
It include preferably organic salt such as quaternary ammonium halides, halogenation quaternary phosphonium containing ionic speciesOxygenIon etc..Ion
Generating compound can be used to improve the ionic strength of polymerisation medium.It is usually ineffective or insufficient effective that ion, which generates compound,
Cause the tertiary organohalogen compounds of raw material monomer.The example that ion generates compound is chlorinated triphenyl methyl.
Diluent
Selected diluent or diluent mixture should provide have to a certain degree polar diluent medium to gather
It closes and is carried out by reasonable rate.In order to meet this requirement, the mixture of single polarity diluent, Polar diluents can be used
Or the mixture of non-polar and polar diluent.In order to reach suitable polarity and solubility, it has been found that if by diluent
Mixing, then the mixture is preferably at least 70% Polar diluents, is based on volume.
Suitable nonpolar diluent components include hydrocarbon and preferred aromatics or cyclic hydrocarbon or their mixture.Such chemical combination
Object includes, for example, hexahydrotoluene, hexamethylene, toluene, carbon disulfide etc..
Suitable Polar diluents include chlorination or fluorinated hydrocarbons, positive structure, branch or cyclic hydrocarbon.Specific chlorinated compound packet
Include liquid diluent such as ethyl chloride, METHYLENE CHLORIDE (dichloro- methane, CH2Cl2), methyl chloride (chloromethane, CH3Cl)、
CHCl3、CCl4, n-butyl chloride, chlorobenzene and other chlorinated hydrocabons.Methyl chloride is desirably used for one embodiment of the present invention
Case.
The fluorinated hydrocarbons that can be used as Polar diluents is hydrofluorocarbon (" HFC "), they are substantially made of hydrogen, carbon and fluorine
Saturation or unsaturated compound, condition are that there are at least one carbon, at least one hydrogen and at least one fluorine.In certain embodiments
In, diluent includes by formula CxHyFzThe hydrofluorocarbon of expression, wherein x is 1-40 perhaps 1-30 perhaps 1-20 or 1-10, or
Person 1-6 perhaps 2-20 perhaps 3-10 or 3-6, the most preferably integer of 1-3, wherein y and z is integer and at least 1.It is suitble to
HFC be disclosed in U.S. Patent number 7,232,872.
When using the mixture of Polar diluents, every kind of diluent (can be based only on polarity dilution by 5-100vol%
The volume of agent) or the amount of 25-50vol% be present in Polar diluents blend, be based only on the volume of Polar diluents.
Polymeric reaction condition
As under usual situation, molecular weight of product by the reaction time, temperature, concentration, reactant property and it is similar because
Element determines.Therefore, different reaction conditions will produce the product of different molecular weight.The synthesis of reaction product needed for realizing；
Therefore, it via the sample monitoring reaction process by periodically being obtained during detection reaction, i.e., is widely used in the art and real
It applies technology shown in example or is sampled by the effluent to flow reactor.
Can be used for the reactor practiced of the present invention include be able to carry out continuous slurry process any conventional reactor and
Those, are incorporated herein by reference disclosed in its equivalent, such as U.S. Patent number 5,417,930.Reactor pump impeller can be with
It is the type pumped up or the type pumped downwards.Reactor has the catalyst system of the invention containing sufficient amount
The polymerization reaction of feed stream of the effect ground catalysis containing monomer, so that producing the polymer with required characteristic of sufficient amount.This
A little commercial reactors are had any different with without volume capacity or pumping/stirring capacity laboratory reactor.
In one embodiment, the feed stream contains the total monomer concentration greater than 30wt% (based on monomer, dilution
The total weight of agent and catalyst system), in another embodiment, it is greater than 35wt%.In another embodiment, the original
Material stream is by the monomer concentration containing 35wt%-50wt%, the total weight based on monomer, diluent and catalyst system.
The reaction condition will enable required temperature, pressure and residence time effectively maintain reaction medium liquid simultaneously
Produce the required polymer with required characteristic.Raw material monomer material is typically essentially free of under polymerization conditions adversely
With any impurity of catalyst reaction.For example, raw material monomer preferably should be essentially free of alkali (such as caustic alkali), the change of sulfur-bearing
Close object (such as H2S, COS and organic mercaptan, for example, methyl mercaptan, ethanethio), nitrogenous compound, oxygen containing alkali such as alcohols etc..
Polymeric reaction temperature suitably becomes according to target polymer molecular weight and the monomer to be polymerize and standard technology
The considerations of amount and economic aspect (such as rate, temperature control etc.), selects.The temperature of polymerization in one embodiment ,-
10 DEG C between the freezing point of polymerization system, in another embodiment, be -25 DEG C to -120 DEG C.In another embodiment party
Case, polymerization temperature are -40 DEG C to -100 DEG C, are -70 DEG C to -100 DEG C in another embodiment.Make us desireing at another
In embodiment, temperature range is -80 DEG C to -100 DEG C.Polymer molecular weight needed for temperature is selected so that realization.Reaction pressure
Power will be in one embodiment 200kPa-1600kPa, be 300kPa-1200kPa in another embodiment,
It is 400kPa-1000kPa in another embodiment.
The ratio between used catalyst (lewis acid) and initiator will be in this field commonly used in carbon cation polymerization
Those of in method.In one embodiment of the invention, catalyst and monomer mole ratio will be 0.10-20, at another
It is 0.5-10 in embodiment.In another desirable embodiment, the ratio between lewis acid and initiator are 0.75-
2.5, or be 1.25-1.5 in another desirable embodiment.The total concentration of initiator in one embodiment,
It is 50-300ppm in reactor, is 100-250ppm in another embodiment.Initiation in catalyst feed stream
The concentration of agent is 500-3000ppm in one embodiment, is 1000-2500ppm in another embodiment.Description
The another way of amount of initiator in the reactor is its amount relative to polymer.There is 0.25- in one embodiment
5.0 moles of polymer/mole initiator have 0.5-3.0 moles of polymer/mole initiator in another embodiment.
The monomer reacted in reactor forms slurry.In one embodiment, in commercial reactors slurry concentration
Equal to or more than=22wt%.In another embodiment, slurry is present in reaction by the concentration equal to or more than 25wt%
In device.The slurry concentration in reactor is less than or equal to 50wt% in yet another embodiment.In yet another embodiment,
Slurry is present in reactor by 22-40wt%.And in yet another embodiment, slurry concentration is existed by 25-35wt%
In reactor.In another embodiment, slurry concentration is in the range of 25-28wt%.
Raw material monomer stream, catalyst, initiator and diluent engagement sequence be not critical for the present invention.At one
In embodiment, by by initiator and Louis before it will inject flow reactor via catalyst nozzle with standard method
This acid, which is mixed together in cold Polar diluents or cold Polar diluents blend, makes their pre- complexings.Can also use will
Other methods of initiator injection reactor.It is desirable that allow monomer enter reactor when or before entering the reactor
It is not contacted with lewis acid and initiator.
In one embodiment of the invention, by mixing initiator and lewis acid together before injecting reactor
Close in cold diluent -50 DEG C to -98 DEG C at a temperature of contact 0.5 second to a few hours, 1 second to 5 minutes time and permit
Perhaps their pre- complexings.In yet another embodiment, lewis acid and initiator are added separately in reactor.
In one embodiment, the polymerization of isobutene and p-methylstyrene includes several steps.Firstly, providing has
The reactor of impeller of pump that can be pumped up or pump downwards.Impeller of pump is usually driven by motor with measurable amperage
It is dynamic.Reactor is generally equipped with the parallel vertical reaction tube in the collet containing liquid ethylene.Total inner volume, including the pipe,
30 to 50 liters are greater than, therefore is able to carry out the polymerization reaction of extensive volume.Reactor usually utilizes liquid ethylene from institute's shape
At removing polymerization reaction heat in slurry.Impeller of pump keeps slurry, diluent, catalyst system and unreacted monomer consistently to flow
Cross reaction tube.Reactor is added in the feed stream of isobutene and methyl styrene in Polar diluents.Then by catalyst
System is added in feed stream, and the catalyst system has lewis acid existing for the molar ratio with 0.50-10.0 and draws
Send out agent.In commercial reactors, so that the feed stream of monomer and catalyst system contacts with each other, the reaction therefore shape
At the slurry of IPMS rubber, wherein the slurry has the concentration of 22wt%-50wt%.Finally, making to be formed by polymer warp
Reactor is left by exporting or flowing out pipeline, while feed stream being inputted to continue polymerization reaction, thus the company of constituting
Continuous slurry polymerization.Advantageously, the present invention improves this method in many aspects, and what is occurred in final reduction outlet opening passes through pressure
The amount for the blocking that inconsistent or " transition " measures.
Total residence time in the reactor is able to rely on such as catalyst activity and concentration, monomer concentration, raw material note
Enter speed, throughput rate, reaction temperature and required molecular weight to change, and be usually about one minute and five hours it
Between, preferably at about 10-60 minutes.The principal variants for controlling the residence time are raw material monomer injection rates.From the present invention one
The polymer that embodiment obtains is that there is the molecular weight distribution of about 2-5 and 200,000 to 2,000,000 exemplary to glue
The isobutene of molecular weight-p-methylstyrene polymer.This product can undergo subsequent halogenation and obtain halogen polymer.
Embodiment
The present invention is described in the range of following experiment.By stainless steel construction and it is being designed to allow for monomer and catalyst
Raw material be introduced into and the laboratory scale flow reactor of polymer product being continuously withdrawn in polymerize.By being mounted on
Mixing is provided on stainless steel shaft and by the triplicate blade impeller of exterior motor driving.Motor is operated with 1200-1600rpm.It is anti-
Device is answered to be equipped with thermocouple to monitor the temperature of reactor content.By the way that the reactor of assembling is immersed in inert-atmosphere glove box
In interior pentane or isohexane bath, reactor is cooled to required reaction temperature.The temperature of the hydrocarbon bath of stirring is controlled to 2 DEG C
It is interior.The whole devices contacted with reaction medium realization liquid are dried at 120 DEG C before the use and are cooled down in nitrogen atmosphere.
By allow gas pass through three stainless steel columns containing barium monoxide by isobutene (can from Matheson Tri-Gas or
ExxonMobil Chemical Company is obtained) and chloromethane it is dry and as liquid condensation and collection in glove box.
It is dry HFA 134a (134a) by allowing gas to flow through three stainless steel columns containing 3A molecular sieve, and in glove box
It is middle to be condensed and collect as liquid.P-methylstyrene is distilled before the use.By low in chloromethane or 134a
It is dissolved into gas HCl in the condensed fluid and prepares HCl solution.These, which are measured, by standard titration technique prepares solution
In HCl concentration.In the examples below, the diluent composition of referred to as " blend " is the 50/ of 134a and chloromethane
50wt/wt mixture.
Slurry copolymerization is carried out by preparing monomer and catalyst raw material first.Raw material monomer prepares in glass or metal reservoir
In and include isobutene, p-methylstyrene and selected diluent.It is that each copolymerization prepares catalyst in individual reservoir
Raw material.Catalyst raw material is prepared by the hydrocarbon solution of the raw material HCl solution and alkyl aluminium halide that add predetermined amount.It is poly- in order to start
Test is closed, initial monomer raw material is also prepared for and reactor is added.Monomer concentration in this initial charge is 5wt% isobutene.
P-methylstyrene is also added to this by with the comparable wt% value of the ratio between isobutene/p-methylstyrene in feedstock blend
In kind initial monomer raw material.It is bathed using the quenching hydrocarbon of glove box and all raw materials is cooled to temperature identical with reactor.
The polymerization in blend is carried out under about -75 DEG C ± 3 DEG C of temperature of reactor, while being grasped at -95 DEG C ± 3 DEG C
Make the polymerization in chloromethane.At the beginning of polymerization, bath temperature is reduced several times to provide the bath and reactor content
Initial temperature differences between object.By introducing catalyst started copolymer.Rate of catalyst flow is controlled to build between reactor and the bath
The constant temperature difference is found to reach the target polymerization temperature of test.Optionally, bath temperature is reduced to help to realize polymerization temperature target.Pass through
The formation of the polymer beads (sludge particles) of precipitating determines addition of the raw material monomer from reservoir.Continue the test until reservoir
In raw material monomer use up or until consuming the desired amount of raw material monomer.In general, the average monomer in these tests turns
Rate is more than 75%, sometime up to 99%.
Observation is made during test, pays attention to the quality and its apparent viscosity of slurry.Once reaction reaches stable state, just collect
Slurry sample is formed with measuring slurry concentration and sludge particles.The slurry in sampling reactor can also be passed through in off-test
Measure sludge particles composition.
Sludge particles, which are collected, by the vacuum filter of slurry measures sludge particles composition.Filter plant includes dynamic vacuum
Source, the cold-trap and stainless steel sintering feed (2 micron porosity) for collecting isolated diluent.By by the sintering feed of the precooling
It immerses in cold slurry and collects particle.Once sludge particles ball is formed around sintering feed, just from slurry remove sintering feed simultaneously from
Between sludge particles and surrounding continuously removes diluent.Out of slurry removes collected particle several seconds and ought no longer from
When material extracts diluent, promptly transfer particle sample is to measure the weight of sample.Heating and dry sample in vacuum drying oven
Then product are weighed with removing diluent from polymer.Polymer weight fractin in the isolated sludge particles of following measurement: it uses
The original weight of relatively more collected " dry " sludge particles of following formula and the weight of separated and dry polymer: in sludge particles
Polymer weight fractin=drying polymer weight/separation sludge particles weight.Separated sludge particles
Weight includes polymer and the total weight for pressing from both sides attached diluent.
The present invention and the result of comparison polymerization are given in the table below.
Table
Test 1 and 2 is comparison aggregation test, and test 3 and 4 is within the scope of the present invention.It can be mentioned from the data group in upper table
Take multiple conclusions.The slurry formed using EASC/HCl catalyst system is fluid and stabilization under 20wt% slurry concentration, and
Under identical wt% slurry concentration, when using EADC/HCl catalyst system, slurry is in unstable edge.Work as use
The change of slurry characteristics allows compared with when using EADC/HCl catalyst system in slurry when EASC/HCl catalyst system
Concentration improves about 25% lower operation reactor.The improvement of slurry weight is consistent with the result of sludge particles composition analysis, wherein
EASC/HCl catalyst system generates the particle for containing more heteropolymer and less diluent.
As for having the higher silt in sludge particles than the commercial reactors for the higher turbulent flow that can be replicated in the lab
What slurry concentration and polymer weight fractin were to be expected to.As a comparison, for isobutene/isoprene polymerization, commercial slurry is dense
Degree reaches only 22wt%'s using the laboratory polymerization of same catalyst and polymerisation medium in 30wt% or close to 30wt%
Maximum can operate slurry concentration, and the slurry concentration of laboratory polymerization reduces about 25%.Therefore, the above laboratory polymerization is tried
Test 3 and 4, in commercial reactors, stable slurry concentration will be expected to 25-28wt%, be significantly higher than in commercial reactors with
The 20wt% of preceding acquisition.For comparative experiments room aggregation test 1 and 2, in commercial reactors, stable slurry concentration will be expected
For 20wt% to less than 25wt%.Although the commercial comparison of test 1 may be close to 25wt% slurry concentration, slurry is unstable
Fixed and the ratio between polymer and initiator are higher than desired ratio significantly.
Industrial applicibility
The resulting polymer of the present invention is comprising C4-C7Isomonoolefin, for example, isobutene and contain at least 80%, more alternatively
At least alkylstyrene comonomer of 90wt% para-isomer, such as the copolymer of p-methylstyrene.In any implementation
In scheme, polymer can be ethylene or C3-C6Alpha-olefin and contain at least 80%, or the alkane of at least 90wt% para-isomer
Base styrene co-monomer, such as the random elastomeric copolymer of p-methylstyrene, wherein degree of randomness is by ring-alkylated styrenes
It introduces characteristic restriction and the polymer is not block copolymer.Illustrative material may be characterized as comprising below along polymerization
The polymer of the monomeric unit at object chain interval:
Wherein R and R1It is independently hydrogen, low alkyl group, such as C1-C7Alkyl and primary or secondary alkyl halide.
In certain embodiments, there is the random copolymer substantially homogeneous compositional to be distributed so that the polymer
At least 95wt% have below to alkylstyrene content: it is described to alkylstyrene content at average pair of the polymer
Within the 10% of alkylstyrene content.Illustratively polymer is characterized in that through gel permeation chromatography measurement less than 5,
Or the narrow molecular weight distribution (Mw/Mn) less than 2.5,200,000 to 2,000,000 illustrative viscosity average molecular weigh and
The illustrative number-average molecular weight of 25,000-750,000.
The polymer can be functionalised after polymerisation or halogenation.Halogenation can carry out in any manner, and this
Invention is not limited herein by Halogenation process.The method of polymer disclosed in halogenation is disclosed in U.S. Patent number 5,670,582.
In one embodiment, halogen polymer has 20-70 (ML 1+8, at 125 DEG C), in another embodiment, 25-55
Mooney viscosity.Halogen wt% is 0.1-10wt% in one embodiment, is 0.5- in another embodiment
5wt%, the weight based on halogen polymer.In yet another embodiment, the halogen wt% of halogen polymer is 1-
2.5wt%.
In one embodiment, brominated poly- (isobutylene-co-p-methylstyrene) " BIMSM " polymer is general
Total amount containing 0.1-5mol% bromometllylstyrene group, relative to the unit of monomer derived in the copolymer.Another
In a embodiment, it is in yet another embodiment 0.3-2.8mol% that the amount of Bromomethyl groups, which is 0.2-3.0mol%,
It is 0.4-2.5mol% in another embodiment, is in yet another embodiment 0.3-2.0mol%, wherein catering to the need
Range can be any combination of any upper limit Yu any lower limit.According to another representation method, the weight based on polymer is shown
Example property copolymer includes 0.2-10wt% bromine, in another embodiment 0.4-6wt% bromine, in another embodiment 0.6-
5.6wt%, halogen substantially free of ring halogen or in the polymer backbone.In one embodiment, the atactic polymerization
Object is C4-C7Unit derived from unit derived from isoalkene (or isomonoolefin), p-methylstyrene and to (halomethylstyrene)
The copolymer of derivative unit, wherein described be present in the polymer by 0.4-3.0mol% to (halomethylstyrene) unit
In, total based on p-methylstyrene and wherein unit derived from the p-methylstyrene in one embodiment, is pressed
3-15wt% is existed, the total weight based on the polymer in another embodiment by 4-10wt%.In another reality
It applies in scheme, is to (bromometllylstyrene) to (halomethylstyrene).
In certain embodiments, IPAS or halogenation IPAS can form blend mistake with other elastomers or polymer
It is blended in journey.Other elastomers as one group are " general purpose rubbers ".
General purpose rubber (commonly referred to as commercial rubber) can be usually provide high-intensitive and good abrasion together with low lag and
Elastomeric any rubber.Because these elastomers generally have the patience of difference to heat and ozone, these elastomers are mixed
Antidegradant is required in the blend of conjunction.
The example of general purpose rubber includes natural rubber (NR), polyisoprene rubber (IR), poly- (styrene-co-fourth
Diene) rubber (SBR), polybutadiene rubber (BR), poly- (isoprene-co-butadiene) rubber (IBR) and styrene-it is different
Pentadiene-butadiene rubber (SIBR) and their mixture.Ethylene-propylene rubber (EPM) and Ethylene-Propylene-Diene rubber
(EPDM) and their mixture is also commonly referred to as general purpose resilient body.
In another embodiment, the composition can also include natural rubber.Natural rubber of the present invention in accordance with
The embodiment needed is selected from Malaysian rubber such as SMR CV, 5 SMR, SMR 10, SMR 20 and SMR 50 and theirs is mixed
Object is closed, wherein the natural rubber has 30-120,100 DEG C of Mooney viscosities (ML1+4) of more preferable 40-65.Present document relates to
Mooney viscosity test is according to ASTM D1646.
In another embodiment, the elastic composition can also include polybutadiene (BR) rubber.It is described poly-
The Mooney viscosity (ML 1+4) that butadiene rubber measures at 100 DEG C can be 35-70, be 40- in another embodiment
About 65, it is 45-60 in yet another embodiment.So-called " cis polybutadiene " or " high-cis polybutadiene " refer to
Using Isosorbide-5-Nitrae-cis polybutadiene, wherein the amount of cis component is at least 95%.
In another embodiment, the elastic composition can also include polyisoprene (IR) rubber.It is described
The Mooney viscosity (ML 1+4) that polyisoprene rubber measures at 100 DEG C can be 35-70, in another embodiment,
It is in yet another embodiment 45-60 for 40- about 65.
In another embodiment, the elastic composition can also include the rubber of the unit of ethylene and propylene derived
Glue such as EPM and EPDM are as suitable added rubber.The example for the comonomer being suitble in manufacture EPDM is ethidine drop
Bornylene, 1,4- hexadiene, dicyclopentadiene and other.These rubber are in RUBBER TECHNOLOGY, P260-283
(1995) it is described in.Suitable ethylene-propylene rubber can be used as VISTALONTM(ExxonMobil Chemical
Company, Houston, TX) it is commercially available.
In yet another embodiment, the elastic composition may include ethylene/alpha-olefin/diene ternary polymerization
Object.The alpha-olefin is selected from C3-C20Alpha-olefin, wherein it is preferred that propylene, butylene and octene, most preferably propylene.The diene component
Selected from C4-C20Diene.The example of suitable diene includes the alkene that straight chain, hydrocarbon diene or the cycloalkenyl containing 6-15 carbon atom replace
Hydrocarbon.Specific example includes (a) straight chain acyclic diene such as 1,4- hexadiene and 1,6- octadiene；(b) branched-chain acyclic diene is for example
5- methyl-1,4- hexadiene；3,7- dimethyl -1,6- octadiene；3,7- dimethyl -1,7- octadiene；With
The mixed isomers of dihydromyricene and dihydroocinene；(c) single ring alicyclic dienes, such as 1,3- ring penta 2
Alkene；1,4- cyclohexadiene；12 carbon diene of 1,5- cyclo-octadiene and 1,5- ring；(d) polycyclic alicyclic fusion and bridging cyclic diolefine
Such as tetrahydroindene；Methyl-tetrahydro indenes；Dicyclopentadiene (DCPD)；Bicyclic-(2.2.1)-hept- 2,5- diene；Alkenyl, alkylidene radical,
Cycloalkenyl and cylcoalkyliene norbornenes, such as 5- methylene -2- norbornene (MNB), 5- acrylic -2- norbornene, 5-
Isopropylidene -2- norbornene, 5- ethidine -2- norbornene (ENB), 5- (4- cyclopentenyl) -2- norbornene, 5- hexamethylene
Pitch base -2- norbornene and 5- vinyl -2- norbornene (VNB)；(e) alkene that cycloalkenyl replaces, such as allyl basic ring
Hexene, vinyl cyclo-octene, allyl cyclodecene, vinyl cyclododecene.Example further include dicyclopentadiene, 1,4- oneself two
Alkene, 5- methylene -2- norbornene and 5- ethidine -2- norbornene.The example of diene is 5- ethidine -2- norbornene；
1,4- hexadiene, dicyclopentadiene and 5- vinyl -2- norbornene.
In another embodiment, auxiliary elastomer is such as butadiene-acrylonitrile of the specific rubber containing polar functional group
Rubber (NBR or nitrile rubber), the i.e. copolymer of 2- acrylonitrile and 1,3-butadiene.Nitrile rubber can have in a reality
It applies in scheme, 10-50wt%, in another embodiment, 15-40wt%, in yet another embodiment, 18-35wt%
Acrylonitrile content.Mooney viscosity can be 30-90 in one embodiment, be 30-75 (1 in another embodiment
+ 4,100 DEG C, ASTM D1646).
In another embodiment, auxiliary elastomer is the derivative such as hydrogenation of NBR or carboxylated or styrene
The nitrile rubber of change.Butadiene-acrylonitrile-styrene rubber (SNBR, or " ABS " rubber), i.e. 2- acrylonitrile, 1,3-butadiene
It can have in one embodiment with the copolymer of styrene, 10-40wt%, in another embodiment, 15-
30wt%, in yet another embodiment, the acrylonitrile content of 18-30wt%.The styrene-content of SNBR copolymer can be
It is 15wt%-40wt% in one embodiment, is 18wt%-30wt%, in another reality in another embodiment
It applies in scheme, is 20-25wt%.Mooney viscosity can be in one embodiment 30-60 (1+4,100 DEG C, ASTM
It D1646), in another embodiment, is 30-55.These rubber are common in the art.
In yet another embodiment, auxiliary elastomer be Halogen group elements specific rubber such as polychlorobutadiene (CR, or
Chloroprene rubber), i.e. the homopolymer of 2- chloro-1,3-butadiene.Mooney viscosity can be 30-110 in one embodiment,
In another embodiment, it is 35-75 (1+4,100 DEG C, ASTM D1646).These rubber are common in the art.
Elastic composition can have two or more elastomers.The elastomer (one or more) can also be with
Other materials or polymer combine.
In another embodiment, not instead of by IPAS polymer with it is auxiliary elastomer blended, IPAS can be polymerize
Object and halogenation IPAS polymer and thermoplastic resin are to form dynamic vulcanization alloy.Term as used herein " thermoplasticity
Resin " refers to upon exposure to high temperature usually softening, or melts and work as that be restored to its when being cooled to compared with low temperature or room temperature original
The material of state.Thermoplastic resin be different from when undergoing heating via crosslinking or solidify and the thermosetting property or elastomer material that solidify
Material.Suitable thermoplastic resin includes, but are not limited to polyamide, polyester, polycarbonate, polysulfones, polyacetals, polylactone, propylene
Nitrile-butadiene styrene resin, polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrile resin, phenylethylene-maleic anhydride resin, virtue
Adoption ketone and ethylene-vinyl alcohol resin.Suitable thermoplastic resin is further disclosed in US 5,453,465 and US 6,907,
In 911.
Elastic composition comprising IPAS or halogenation IPAS can also include various other components and can be optionally
Cured and formation is finally manufactured into the cured elastomer composition of final use product.
For example, elastic composition can optionally include:
A) at least one filler is for example, calcium carbonate, clay, mica, silica, silicate, talcum, titanium dioxide, shallow lake
Powder, wood powder, carbon black or their mixture；
B) at least one inorganic nano clay is for example, montmorillonite, nontronite, beidellite, chromium-rich nontronite
(volkonskoite), synthetic soapstone (laponite), hectorite, saponite, sauconite, magadiite
(magadite), kenyaite (kenyaite), magnesium-rich smectite (stevensite), vermiculite, galapectite, aluminate oxidation
Object, hydrotalcite or their mixture, are optionally pocessed with modifying agent and form nanoclay；
C) at least one processing oil is for example, aromatic naphtha, naphthenic oil, paraffin oil or their mixture；
D) at least one processing aid is for example, plastic body, polybutene, poly & Alpha ,-olefin oil or their mixture；
E) at least one solidification package (cure package) or curing agent or in which the composition have been subjected to
Lack a kind of processing and generate solidification composition filling, such as zinc oxide, zinc stearate, stearic acid, sulphur or their mixture；Or
F) any combination of a-e.
The elastic composition can squeeze out, compression moulding, blow molding, be molded and be laminated into various molded articles, including fiber,
Film, layered product, layer, industrial part such as automobile component, apparatus shell, the consumer goods, packaging etc..
Specifically, the elastic composition is in the product for various tire applications such as truck tyre, motor bus
It is useful in tire, automobile tire, motorcycle tyre, off-road tire, aero tyre etc..The elastic composition can be with
Manufacture into the liner of the component such as tire of finished product or finished product.The product can be selected from inner liner, airtight film, film, layer (microbedding
And/or multilayer), liner, inner tube, side wall, tyre surface, capsule etc..
In another kind application, the elastic composition can be used for air cushion, gas spring, airbag, hose, bumping bag
With belt such as conveyer belt or automobile belt.
They can be used for molding the rubber components of processing and and in vehicle suspension vibrater, automobile exhaust hanger and vehicle body
There is extensive use on fixed frame.
In addition, the elastic composition also is used as adhesive, caulking agent, the caulking compound of sealant and glazing.
They also act as the plasticizer in rubber formulation；The component for stretching the composition of cladding film is made；Point as lubricant
Powder；With for be poured and cable filler.
In other application also, elastomer of the invention (one or more) or elastic composition can also be used in mouth
Fragrant sugar, and it is used for medical applications such as drug plug and closure, the coating of medical instrument and the arts of paint roller.
Therefore present disclosure provides following embodiments:
A. it prepares derived from C4-C7The polymerization of the polymer of isoolefin monomer and alkyl-styrene monomer, the side
Method includes:
A) feed stream is provided in reactor, the feed stream includes the isoalkene, alkyl-styrene list
Body, Polar diluents or Polar diluents mixture and catalyst system, and
B) feed stream is made to be in contact with each other in the reactor thus the monomer formed in stable slurry it is poly-
Object is closed, wherein amount of the polymer in the slurry generates the slurry concentration for being greater than 22wt%；
B. it prepares derived from C4-C7The polymerization of the polymer of isoolefin monomer and alkyl-styrene monomer, the side
Method includes:
A) feed stream is provided in reactor, the feed stream includes the isoalkene, alkyl-styrene list
Body, Polar diluents or Polar diluents mixture and catalyst system comprising lewis acid and initiator, and
B) feed stream is made to be in contact with each other in the reactor thus the monomer formed in stable slurry it is poly-
Object is closed, wherein being formed by the ratio between mole of polymer and initiator in 0.25-4.0 moles of polymer/mole initiator model
In enclosing；
C. the polymerization of embodiment A or B, wherein the slurry has the slurry concentration of 25-35wt%；
D. the polymerization of embodiment A or B, wherein the slurry has the slurry concentration equal to or more than 25wt%；
E. the polymerization of embodiment A or B, wherein the slurry concentration is in the range of 22-40wt%；
F. any combination of polymerization of any one of embodiment A-E or embodiment A-E, wherein being formed by
The ratio between mole of polymer and initiator is no more than 4 moles of polymer/1 mole initiator；
G. any combination of polymerization of any one of embodiment A-F or embodiment A-F, wherein being formed by poly-
The ratio between mole of conjunction object and initiator is in the range of 0.25-4.0 moles of polymer/1 mole initiator；
H. any combination of polymerization of any one of embodiment A-G or embodiment A-G, wherein the catalyst
System includes lewis acid and initiator；
I. the polymerization of embodiment H, wherein lewis acid is with general formula RnMX3-nThe 13rd race's lewis acid,
Middle M is the 13rd race's metal, and R is selected from C1-C12Alkyl, aryl, aralkyl, alkaryl and naphthenic base monovalent hydrocarbon；N is 0-3
Integer；X is independently selected from the halogen of fluorine, chlorine, bromine and iodine；
J. the polymerization of embodiment H, wherein the lewis acid is ethylaluminum sesquichloride, aluminium bromide, tri-chlorination
Boron, diethylaluminum chloride, chlorodimethylalumiu and di-isobutyl aluminum chloride or their mixture；
K. the polymerization of embodiment H, wherein initiator is HCl, water or has general formula:
Wherein X is halogen；R1Selected from C1-C8Alkyl and C2-C8Alkenyl；R3Selected from C1-C8Alkyl, C2-C8Alkenyl and octadecyloxy phenyl
Base；And R2Selected from C4-C200Alkyl, C2-C8Alkenyl, phenyl, phenylalkyl, alkyl phenyl, C3-C10Naphthenic base and
Wherein X is halogen；R5Selected from C1-C8Alkyl and C2-C8Alkenyl；R6Selected from C1-C8Alkyl, C2-C8Alkenyl and octadecyloxy phenyl
Base；R4Selected from phenylene, xenyl, α, ω-diphenyl alkane and-(CH2)n, wherein n is the integer of 1-10；Wherein R1、R2With
R3Adamantyl or borneol ring system can also be formed, the X group is in tertiary carbon position；
L. any combination of polymerization of any one of embodiment A-K or embodiment A-K, wherein by oxygen-containing chemical combination
Object is provided containing ionic species into the reactor；
M. the polymerization of embodiment L, wherein the oxygenatedchemicals is alcohol or ester；
N. any combination of polymerization of any one of embodiment A-M or embodiment A-M, wherein the isoolefine
Hydrocarbon monomer is isobutene, isobutene, 2- methyl-l- butylene, 3-methyl-1-butene, 2- methyl-2-butene, 1- butylene, 2- fourth
Alkene, methyl vinyl ether, indenes, vinyl trimethylsilane, hexene or 4-methyl-1-pentene；
O. any combination of polymerization of any one of embodiment A-N or embodiment A-N, wherein the alkyl-
The alkyl substitution of styrene is C1-C7Alkyl；
P. any combination of polymerization of any one of embodiment A-O or embodiment A-O, wherein additional list
Body can reside in for polymerizeing with the isoalkene and the ring-alkylated styrenes in the feed stream, the additional monomer
For C4-C14Polyene；
Q. any combination of polymerization of any one of embodiment A-P or embodiment A-P, wherein the polarity
Diluent mixture is the mixture or at least 70vol% Polar diluents and apolar diluent of at least two Polar diluents
Mixture；
R. pass through the isoalkene-of any combination of method manufacture of any one of embodiment A-Q or embodiment A-Q
Ring-alkylated styrenes polymer；
S. the polymer of embodiment R, wherein the polymer can also contain C4-C14Unit derived from polyene；
T. the polymer of embodiment R or S, wherein being blended the polymer to form composition, the composition can
With comprising:
A) at least one to be selected from calcium carbonate, clay, mica, silica, silicate, talcum, titanium dioxide, starch, wood
The filler of powder, carbon black or their mixture；
B) at least one inorganic nano clay or nanoclay；
C) at least one processing oil；
D) at least one processing aid selected from plastic body, polybutene, poly & Alpha ,-olefin oil or their mixture；
E) at least one curing agent；
F) auxiliary elastomer；
G) thermoplastic resin；Or
H) any combination of a-g；
U. any combination of polymer of any one of embodiment R-T or embodiment R-T, wherein the composition
It can be used for tire flap, tyre capsule, curing bag, hose, conveyer belt or drug plug.
Claims (6)
1. preparation is derived from C4-C7The polymerization of the polymer of isoolefin monomer and alkyl-styrene monomer, the method packet
It includes:
A) feed stream is provided in reactor, the feed stream includes the C4-C7Isoolefin monomer, alkyl-styrene
Monomer, Polar diluents or Polar diluents mixture and catalyst system, wherein the catalyst system be ethyl aluminum dichloride,
HCl and selected from alcohol, ester or containing the component of ionic species, it is described to be selected from quaternary ammonium halides, halogenation quaternary phosphonium, oxygen containing ionic species
The organic salt of ion；With
B) feed stream is made to be in contact with each other in the reactor so that the monomer forms polymer in slurry, wherein
Amount of the polymer in the slurry generates the slurry concentration for being greater than 22wt%,
The ratio between mole for the polymer that wherein every mole of HCl is formed is no more than 4 moles of polymer/1 mole HCl.
2. the polymerization of claim 1, wherein the slurry concentration is in the range of 22-40wt%.
3. the polymerization of claims 1 or 2, wherein the alkyl of the alkyl-styrene monomer is substituted by C1-C7Alkyl.
4. the polymerization of claims 1 or 2 is used for and the C wherein additional monomer is present in the feed stream4-C7
Isoolefin monomer and alkylstyrene monomers polymerization, the additional monomer are C4-C14Polyene.
5. the polymerization of polymer of the preparation derived from monomer and alkyl-styrene monomer, which comprises
A) feed stream is provided in reactor, the feed stream includes the monomer, alkyl-styrene monomer, polarity
Diluent or Polar diluents mixture and catalyst system, wherein the catalyst system is ethyl aluminum dichloride, HCl and is selected from
Alcohol, ester or the component containing ionic species, it is described to be selected from quaternary ammonium halides, halogenation quaternary phosphonium, oxonium ion containing ionic species
Organic salt；With
B) feed stream is made to be in contact with each other in the reactor so that the monomer forms polymer in slurry, wherein
Amount of the polymer in the slurry generates the slurry concentration for being greater than 22wt%,
Wherein every mole of HCl formed polymer the ratio between mole be no more than 4 moles of polymer/1 mole HCl, and
Wherein the monomer be selected from isobutene, 2- methyl-l- butylene, 3-methyl-1-butene, 2- methyl-2-butene, 1- butylene,
2- butylene, methyl vinyl ether, indenes, vinyl trimethylsilane, hexene or 4-methyl-1-pentene.
6. the polymerization of claim 5, wherein the alkyl of the alkyl-styrene monomer is substituted by C1-C7Alkyl.
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| US12/791,520 | 2010-06-01 | ||
| US12/791,520 US9079990B2 (en) | 2010-06-01 | 2010-06-01 | Methods of production of alkylstyrene/isoolefin polymers |
| CN201180026851.8A CN102933621B (en) | 2010-06-01 | 2011-04-27 | The preparation method of ring-alkylated styrenes/isoolefin polymer |
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| CA2853063A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Polyisobutylene prepared at high velocity and circulation rate |
| RU2699539C2 (en) * | 2013-12-23 | 2019-09-06 | Арланксео Сингапур Пте. Лтд. | Highly pure halogenated rubber |
| JP6523297B2 (en) * | 2013-12-23 | 2019-05-29 | アランセオ・シンガポール・プライヴェート・リミテッド | Rubber containing adjustable levels of metal-containing antiflocculant |
| WO2015164972A1 (en) | 2014-04-30 | 2015-11-05 | Lanxess Inc. | Diluent for the production of butyl rubber |
| CN107614555B (en) | 2015-05-26 | 2020-03-20 | 株式会社钟化 | Method for producing thermoplastic elastomer and thermoplastic elastomer |
| JP6943026B2 (en) | 2017-06-08 | 2021-09-29 | 日本精工株式会社 | Carburizing method for rolling bearings and manufacturing method for rolling bearings |
| WO2019011813A1 (en) * | 2017-07-12 | 2019-01-17 | Arlanxeo Deutschland Gmbh | Process for the production of isoolefin polymers with improved initiator system preparation |
| JP7229420B2 (en) * | 2020-04-08 | 2023-02-27 | エルジー・ケム・リミテッド | Catalyst composition and method for producing isobutene-based polymer using the same |
| CN111393556B (en) * | 2020-05-15 | 2023-04-07 | 山东京博中聚新材料有限公司 | Isomonoolefin-alkylstyrene copolymer and preparation method thereof |
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| US5430118A (en) | 1988-05-27 | 1995-07-04 | Exxon Chemical Patents Inc. | Para-alkylstyrene/isoolefin copolymers having substantially homogeneous compositional distribution |
| CA1338546C (en) * | 1988-05-27 | 1996-08-20 | Kenneth William Powers | Para-alkylstyrene/isoolefin copolymers |
| US4946899A (en) | 1988-12-16 | 1990-08-07 | The University Of Akron | Thermoplastic elastomers of isobutylene and process of preparation |
| ATE152139T1 (en) | 1991-07-29 | 1997-05-15 | Exxon Chemical Patents Inc | POLYMERIZATION REACTOR |
| US5244961A (en) | 1991-09-19 | 1993-09-14 | Exxon Chemical Patents Inc. | Thermoplastic compositions and process for preparing the same |
| US5670582A (en) | 1996-07-24 | 1997-09-23 | Exxon Chemical Patents Inc. | Process for halogenation of isomonoolefin/para-alkylstyrene copolymers |
| US6858690B2 (en) | 1999-11-15 | 2005-02-22 | Exxonmobil Chemical Patents Inc. | Process for polymerizing cationically polymerizable monomers |
| EP1237950B1 (en) * | 1999-11-15 | 2005-05-04 | ExxonMobil Chemical Patents Inc. | Production of isobutylene copolymers |
| US6939933B2 (en) | 2000-12-20 | 2005-09-06 | Exxonmobil Chemical Patents Inc. | Process for polymerizing cationically polymerizable monomers |
| US6376598B1 (en) | 2000-06-15 | 2002-04-23 | Exxon Mobil Chemical Patents Inc. | Thermoplastic blend |
| CA2493729A1 (en) * | 2002-08-13 | 2004-02-19 | Exxonmobil Chemical Patents Inc. | Process for polymerizing cationically polymerizable monomers |
| RU2362786C2 (en) * | 2002-12-20 | 2009-07-27 | Эксонмобил Кемикэл Пейтентс Инк. | Methods of polymerisation |
| WO2004058836A1 (en) | 2002-12-20 | 2004-07-15 | Exxonmobil Chemical Patents Inc. | Polymers with new sequence distributions |
| US7582715B2 (en) * | 2002-12-20 | 2009-09-01 | Exxonmobil Chemical Patents Inc. | Polymers substantially free of long chain branching |
| RU2346010C2 (en) * | 2002-12-20 | 2009-02-10 | Эксонмобил Кемикэл Пейтентс Инк. | Polymerisation techniques |
| EP1572752B1 (en) | 2002-12-20 | 2014-08-13 | ExxonMobil Chemical Patents Inc. | Polymerization processes |
| US7425601B2 (en) | 2002-12-20 | 2008-09-16 | Exxonmobil Chemical Patents Inc. | Polymers with new sequence distributions |
| CN1972974B (en) * | 2004-06-25 | 2010-05-12 | 埃克森美孚化学专利公司 | Polymerization processes using hydrofluorocarbons |
| US7402636B1 (en) | 2007-03-23 | 2008-07-22 | Exxonmobil Chemical Patents Inc | Method and apparatus for decreasing polymer deposition |
| US7981991B2 (en) * | 2007-04-20 | 2011-07-19 | Exxonmobil Chemical Patents Inc. | Separation of polymer slurries |
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| CA2801806A1 (en) | 2011-12-08 |
| EP2576640A1 (en) | 2013-04-10 |
| US9079990B2 (en) | 2015-07-14 |
| CN102933621A (en) | 2013-02-13 |
| CN106008776A (en) | 2016-10-12 |
| US20110294924A1 (en) | 2011-12-01 |
| CN102933621B (en) | 2016-06-01 |
| JP2013527304A (en) | 2013-06-27 |
| SG185595A1 (en) | 2012-12-28 |
| JP5770270B2 (en) | 2015-08-26 |
| CA2801806C (en) | 2015-10-06 |
| RU2012149003A (en) | 2014-05-27 |
| EP2576640B1 (en) | 2017-03-29 |
| RU2562969C2 (en) | 2015-09-10 |
| WO2011152931A1 (en) | 2011-12-08 |
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